Amine salts of the tridecyl esters of sulfobenzoic acid



Patented July 13, 1954 AMINE SALTS OF THE TRIDECYL ESTER/S OFSULFOBENZOIC ACID Milton Kosmin, Dayton, Ohio, assignor to MonsantoChemical Company, St. Louis, Mo., a corporation of Delaware No Drawing.Application September 19, 1952, Serial No. 310,567

12 Claims. 1

The present invention relates to surface-active agents and isparticularly concerned with alkylamine or alkanolamine salts of tridecylsulfobenzoates as new compounds possessing a high degree of utility aswetting-out and lathering agents.

As is known, surface-active agents find wide application in a largenumber of industrial processes, especially in those relating to thetreatment of textiles and other fibrous materials. Among the compoundsheretofore suggested for these and related purposes are the esters ofsulfobenzoic acid and aliphatic alcohols containing from 812 or 18carbon atoms, for example, the octyl, dodecyl, or oleyl sodiumsulfobenzoate as illustrated in U. S. Patents 2,359,291 and 2,423,972. Ihave now found, as a result of comparative tests, that the heretoforeunknown alkylamine or alkanolamine salts of the esters of sulfobenzoicacids and a certain mixture of isomeric tridecyl alcohols are ofoutstanding value, not only for the purpose of assisting in the wettingof textile materials, but also from a lathering standpoint. They areparticularly valuable as tasteless foaming agents in dentifriceformulations, in edible oils adapted for use in mayonnaise preparation,and as tasteless wetting agents in the manufacture of food extracts, e.g., in soluble coiTee extraction, etc. The present sulfobenzoates areobtainable by neutralizing with an alkylamine or an alkanolamine, theacid ester obtained by condensing 2-, 3- or 4-sulfobenzoic acid or anacid halide thereof with an alcohol fraction derived by thecarbonylation and hydrogenation (Oxo) reaction of "the olefinstriisobutylene and tetrapropylene. The alcohol fraction which forms thestarting material for my present esters may be defined as having thestructure ROI-I, wherein R is a primary alkyl radical having an averageof 13 carbon atoms derived from an alcohol formed by the carbonylationand hydrogenation of triisobutylene or tetrapropylene or mixturesthereof.

The present sulfobenzoates may be represented by the following structurehas from 1 to 4 carbon atoms and alkylenepolyamines andpolyalkylenepolyamines having from 2 to 4 amino groups in the moleculeand from 2 to 3 carbon atoms in the alkylene chain. As examples of saltsof tridecyl 2-, 3- or 4-su1fobenzoate having the above formula andprovided by the present invention may be mentioned monoalkylamine saltssuch as the ethylamine, n-butylamine, 2-ethylhexylamine, n-decylamineand tert-dodecylamine salts; the dialkylamine salts such as thedimethylamine, diisopropylamine. din-octylamine and the methylethylaminesalts; the trialkylamine salts such as the trimethylamine,tri-n-butylamine, and tri-tert-amylamine salts; the mono-alkanolaminesalts such as the ethanolamine and the 4-hydroxybutylamine salts, thedi-alkanolamine salts, such as the diisopropanolamine, dimethanolamine,and methanolethanolamine; the tri-alkanolamine salts such as thetriethanolamine and tri-n-propanolamine salts; the alkylene orpolyalkylene polyamine salts such as the ethylenediamine,triethylenetetramine, dipropylenetriamine, and diethylenetriamine salts,and morpholine.

The invention is further illustrated, but not limited, by the followingexample:

EXAMPLE Into a reaction vessel equipped with mechanical stirrer,thermometer, and drying tube there was placed 310.5 g. (1.5 mole) of anisomeric mix ture of tridecyl alcohols boiling within the range of 252.8C.-2'73.9 C. and obtained by the Oxo process from a polymeric olefin of12 carbon atoms, carbon monoxide and hydrogen. m-Sulfobenzoic acid(303.0 g.) was heated to 150 C. and then poured into the tridecylalcohol, whereupon the temperature of the reaction mixture rose to 90 C.The resulting mixture was stirred at a temperature of from 90-95 C, for80 minutes and then allowed to cool. At this point the reaction mixturecomprised the substantially pure tridecyl sulfobenzoic acid. It wasdivided into 100 g. portions and each portion was then neutralized tothe pH shown below with an ethanol solution of one of the followingamines:

000R I monoethanolamine to pH 8.1

II triethanolamine to pH 6.55 III N-butylamine to pH 8.5 SO3H.Z IVdiisobutylamine to pH 7.1

in which R is as defined above and in which Z is selected from the classconsisting of mono-, diand trialkylamines in which the alkyl radicalcontains from 1 to 12 carbon atoms, mono-, diand trialkanolamines inwhich the alkanol radical V 2-ethylhexylamine to pH 7.25 VI diethylamineto pH 6.9 VII diethylenetriamine to pH 7.8

The resulting neutralized ethanol solutions were dried with stirringunder reduced pressure (15-20 3 mm.) at a maximum pot temperature of40-45 C. The dried. products comprised the respective amine salts oftridecyl sulfobenzoate. Testing of the surface activity of the driedsalts thus obtained gave the following values:

Surface activity of tridecyl sulfobenzoate amine salts Surface TensionInterfacial Tension dynes/cm. a dynes/cm., at percent ConcenpercentConcen- Amine Salt tration tration monoethanolamine 29. 7 30. 7 31. 32.4 4. 9 7. 4 triethanolamine 31. 6 27. 8 35. 4. 5 7. 5 10. 3n-butylaniine 1 32. 7 32. 4 32.4 1. O O. 6 (l. 8 di-isobutylamine 37. 433. 7 39. 7 4. 6 6.0 10. 3 2-ethylhexylamine 1 32. 0 38.2 36. 6 1. 0 5.3 8. 4 diethylamine. i 34. 3 37 6 40. 8 2. 3 3. 5 4. 6diethylenetriamine 31. 3 32. 4 32. 4 l. O 1. 3 l3. 1

X For surface tension determination there were employed solutions in aliquid paraifinic hydrocarbon known to the trade as Nujol and having asurface tension of 38 dynes/cm. lnteriacial tension was determinedagainst distilled water.

Salt Tested 0.5 0.25 0.125 0.0025 0.03 0.01

monoethanolamine. 3. 7 6. 2 14. 2 36. 8 75.0 180+ triethanolamine 3. 96. 2 15. 5 38. 8 180+ diethylainine 7.8 8. 6 17. 5 58. 7 75. 8 180+ Thewater-soluble monoethanolamine, triethanolamine and diethylamine saltsof sulfobenzoic acid prepared as described above were tested fordetergency by the method described by Jay C. Harris and Earl L. Brown inthe Journal of the American Oil Chemists Society, vol. 27, p. 135-143(1950). By the application of this method it is possible to evaluate thedeterg-ency of a product in terms of any standard detergent. Forconvenience I have compared the detergency of the present and relatedproducts with the detergency of Gardinol WA, which is a commercialdetergent produced by sulfating the alcohols derived by hydrogenation ofcoconut oil fatty acids. The following results were obtained for testsconducted in water of 50 p. p. m. hardness:

C ompound Tested D ggfg f monoethanolaminc 121 triethanolamine 107diethylamine 113 Lather heights, cm.

Salt of Tridecyl Sull'obenzoate Tested At Once monoethanolamine 1 5. 014. 7 triethanolamine 14. 7 14. 5

What I claim is: 1. Surface-active agents having the formula COOR S OaELZ in which R, is a primary alkyl radical having an average of 13carbon atoms derived from an alcohol formed by the carbonylation andhydrogenation of an olefin selected from the class consisting oftriisobutylene and tetrapropylene and mixtures of the same and in whichZ is selected from the class consisting of mono-, diand trialkylaminesin which the alkyl radicals contains from 1 to 12 carbon atoms, mono-,diand trialkanolamines in which the alkanol radi cal has from 1 to 4carbon atoms and alkylenepolyamines and polyalkylenepolyamines havingfrom 2 to 4 amino groups in the molecule and from 2 to 3 carbon atoms inthe alkylene chain, and morpholine.

2. The monoethanolamine salt of the tridecyl ester of sulfobenzoic acid.

3. The triethanolamine salt of the tridecyl ester of sulfobenzoic acid.

4. The n-butylamine salt of the tridecyl ester of sulfobenzoic acid.

5. The 2-ethylhexylamine salt of the tridecyl ester of sulfobenzoicacid.

6. The diethylenetriamine salt of the tridecyl ester of sulfobenzoicacid.

'7. The process of preparing surface-active agents which comprisescontacting a sulfobenzoate having the formula COOR SOaH

wherein R is a primary alkyl radical having an average of 13 carbonatoms derived from an alcohol formed by the carbonylation andhydrogenation of an olefin selected from the class consisting oftriisobutylene, tetrapropylene, and mixtures thereof with an aminecompound selected from the class consisting of mono-, diandtrialkylamines in which the alkyl radical contains from 1 to 12 carbonatoms, mono-, diand trialkanolamines in which the alkanol radical hasfrom 1 to 4 carbon atoms and alkylenepolyamines andpolyalkylenepolyamines having from 2 to 4 amino groups in the moleculeand from 2 to 3 carbon atoms in the alkylene chain and morpholine, andrecovering from the resulting reaction product salts having the formulaCOOR SOaELZ in which R is a primary alkyl radical having an average of13 carbon atoms derived from an alcohol formed by the carbonylation andhydrogenation of an olefin selected from the class consisting oftriisobutylene, tetrapropylene and mixtures thereof and Z is selectedfrom the class consisting of mono-, diand trialkylamines in which thealkyl radical contains from 1 to 12 carbon atoms, mono-, diandtrialkanolamines in which the alkanol radical has from 1 to 4 carbonatoms and alkylenepolyamines and polyalkylenepolyamines having from 2 to4 amino covering the n-butylamine salt of tridecyl sulfobenzoate fromthe resulting reaction product.

11. The process which comprises contacting tridecyl sulfobenzoate with2-ethylhexylamine and recovering the Z-ethylhexylamine salt of trideoylsulfobenzoate from the resulting reaction product.

12. The process which comprises contacting triclecyl sulfobenzoate withdiethyienetriamine and recovering the diethylenetriamine salt oftridecyl sulfobenzoate from the resulting reaction product.

N 0 references cited.

1. SURFACE-ACTIVE AGENTS HAVING THE FORMULA